The present invention relates to a silver halide photographic emulsion and a silver halide photographic light-sensitive material and, more particularly, to a silver halide photographic emulsion with high sensitivity and high graininess and a silver halide photographic light-sensitive material containing the emulsion.
Methods of manufacturing and techniques of using tabular silver halide grains are already disclosed in, e.g., U.S. Pat. No. 4,434,226, U.S. Pat. No. 4,439,520, U.S. Pat. No. 4,414,310, U.S. Pat. No. 4,433,048, U.S. Pat. No. 4,414,306, and U.S. Pat. No. 4,459,353. Advantages such as improvement of the sensitivity/graininess relationship including improvement of the sensitization efficiency obtained by spectral sensitizing dyes are known.
Extensive research has been done to use tabular grains having these advantages in a large size region greatly contributing to the performance of color negative sensitive materials.
Jpn. Pat. Appln. KOKAI Publication No. (hereinafter referred to as JP-A-) 63-220238 has disclosed a technique of increasing the sensitivity and improving the resistance to pressure by introducing dislocations.
Also, as a technique of using metal compounds, U.S. Pat. No. 5,576,172 has disclosed a method of increasing the sensitivity and improving the low illumination intensity failure by using both of group VIII elements and Ir element.
Unfortunately, small formatting of color negative films has advanced as shown in the APS format, so demands on improved image quality cannot be satisfied even by the use of these conventional techniques. Accordingly, a technique of further improving the sensitivity has been desired.
It is an object of the present invention to provide a silver halide photographic emulsion with high sensitivity and high graininess and a silver halide photographic light-sensitive material containing the emulsion.
(1) A silver halide photographic emulsion in which tabular grains having an equivalent-circle diameter of 0.6 xcexcm or more, a thickness of 0.3 xcexcm or less, and an aspect ratio of 2 or more account for 70% or more (in number), wherein each of the tabular grains has a multilayered structure including two or more layers, at least one of the layers contains 1 to 20 mol % of a chloride with respect to the amount of silver forming the layer and each of the tabular grains contain a metal complex represented by formula (C-1) or (C-2) below:
[M1(CN)6-aLa]nxe2x80x83xe2x80x83(C-1) 
[M2(CN)4-bLb]mxe2x80x83xe2x80x83(C-2) 
wherein
M1: Fe, Ru, Re, Os, Ir, or Pt
M2: Pt or Au
L: a ligand except for CN
a: 0, 1, or 2
b: 0, 1, or 2
n: 2-, 3-, or 4-
m: 1- or 2-;
(2) The silver halide photographic emulsion described in item (1) above, wherein dislocation lines are observed in 80% or more (in number) of the tabular grains;
(3) The silver halide photographic emulsion described in item (2) above, wherein the variation coefficient of the equivalent-circle diameters of the tabular grains is 25% or less;
(4) The silver halide photographic emulsion described in any one of items (1) to (3) above, wherein the average aspect ratio of the tabular grains is 8 or more; and
(5) A silver halide photographic light-sensitive material having one or more silver halide emulsion layers on a support, wherein at least one of the emulsion layers contains the silver halide photographic emulsion described in any one of items (1) to (4) above.
The present invention will be described in detail below.
The emulsion of the present invention contains 70% or more (in number) of tabular silver halide grains having an equivalent-circle diameter of 0.6 xcexcm or more. A xe2x80x9ctabular silver halide grainxe2x80x9d is a general term of grains having one twin plane or two or more parallel twin planes or grains which have no twin planes and principally have (110) main surfaces. A xe2x80x9ctwin planexe2x80x9d is a (111) plane on both sides of which all ions at lattice points have a mirror image relationship to each other. When this tabular grain is viewed from the direction perpendicular to the main surface, it looks like a triangle, a square, a hexagon, or a form obtained from a triangle, a square or a hexagon by making each corner thereof roundish. These triangular, square, hexagonal, and circular grains have parallel triangular, square, hexagonal, and circular main surfaces, respectively.
In the present invention, an equivalent-circle diameter is the diameter of a circle having the same area as the projected area of the parallel main surfaces of a grain.
The projected area of a grain can be obtained by measuring the area on an electron micrograph and correcting the magnification.
The thickness of a grain can be easily measured by obliquely depositing a metal on a grain, together with a latex as a reference, measuring the length of the shadow of the latex and the grain in an electron micrograph, and calculating by referring to the length of the shadow of the latex.
In the present invention, the aspect ratio of a tabular grain is the value obtained by dividing the equivalent-circle diameter by the grain thickness. The average aspect ratio is the average value of the aspect ratios of 1,000 or more grains in an emulsion.
The equivalent-circle diameter of each of the tabular grains occupying 70% or more of all the grains in the emulsion of the present invention is preferably 0.6 xcexcm or more, more preferably 0.6 to 5.0 xcexcm, and most preferably 0.8 to 3.0 xcexcm.
The thickness of each of the tabular grains occupying 70% or more of all the grains in the emulsion of the present invention is preferably 0.03 to 0.3 xcexcm, more preferably 0.03 to 0.25 xcexcm, and most preferably 0.05 to 0.20 xcexcm.
The average aspect ratio of each of the tabular grains occupying 70% or more of all the grains in the emulsion of the present invention is 2 or more, preferably 8 to 50, more preferably 8 to 40, and most preferably 8 to 30.
Each of the tabular grains used in the present invention has a multilayered structure including two or more layers, i.e., so to call a core/shell structure. Portions of a grain having different halogen compositions are called xe2x80x9clayersxe2x80x9d. For example, a grain composed of a portion having an iodide content of 20 mol %, i.e., core portion, and a portion having an iodide content of 5 mol %, i.e., a first shell, has a two-layered structure.
Each of the tabular grains used in the present invention has at least one layer containing 1 to 20 mol % of a chloride with respect to the silver amount of the layer. The chloride content is more preferably 1 to 15 mol %, and most preferably 3 to 10 mol %.
When a chloride is contained in at least one layer, the rest of the halogen composition in the layer can have arbitrary bromide and/or iodide content. However, the iodide content is preferably 0 to 35 mol %, more preferably 1 to 20 mol %, and most preferably 2 to 10 mol %.
The composition of each of the tabular grains used in the invention can be silver chlorobromide, silver chloroiodide or silver chloroiodobromide. The chloride content of the silver halides is 0.1 to 10 mol %, preferably 0.1 to 5 mol %, and most preferably 0.1 to 3 mol %. The silver iodide content of the silver halides, if any, is 0.1 to 20 mol %, preferably 0.1 to 15 mol %, and most preferably 0.1 to 10 mol %.
The halogen composition structure of a tabular grain used in the present invention can be checked by combining, e.g., X-ray diffraction, a transmission analytical electron microscope (analytical TEM), EPMA (also called XMA; a method of scanning a silver halide grain by electron rays to detect its silver halide composition), and ESCA (also called XPS; a method of radiating X-rays to spectroscopically detect photoelectrons emitted from the surface of a grain).
The relative standard deviation of the inter-grain silver iodide distribution and silver chloride distribution of a silver halide emulsion of the present invention is not particularly restricted. However, this relative standard deviation is preferably 50% or less, more preferably 35% or less, and most preferably 20% or less.
The halogen contents of individual emulsion grains can be measured by analyzing the composition of each grain by using, e.g., an X-ray microanalyzer. The xe2x80x9crelative standard deviation of the halogen contents of individual grainsxe2x80x9d, explaining taking an example of silver iodide deviation, is the value obtained by dividing the standard deviation of halogen contents, when the silver iodide contents of at least 100 emulsion grains are measured by, e.g., an X-ray microanalyzer, by the average halogen content and multiplying the quotient by 100. A practical method of measuring the halogen contents of individual grains is described in, e.g., E.P. 147,868A, the disclosure of which is herein incorporated by reference.
If the relative standard deviation of the silver iodide contents and silver chloride contents of individual grains is large, these grains have different appropriate points in chemical sensitization. Consequently, it becomes impossible to fully utilize the properties of all emulsion grains. Additionally, the inter-grain relative standard deviation of the number of dislocations tends to increase.
A silver iodide content Yi (mol %) and an equivalent-sphere diameter Xi (micron) of each grain and silver chloride content Yc (mol %) and an equivalent-sphere diameter Xc (micron) of each grain sometimes have a correlation. However, it is desirable not to have any correlation.
It is sometimes possible to obtain more preferable effects by using monodisperse tabular grains. Although the structure and the method of manufacturing monodisperse tabular grains are described in, e.g., JP-A-63-151618, the disclosure of which is herein incorporated by reference, the shape of the grains will be briefly described below. That is, tabular grains having two parallel main surfaces occupy 70% or more of the total projected area of all the grains in an emulsion. Each of the main surface of the tabular grains has a shape, that is viewed from the direction perpendicular to the main surface, in which the ratio of an edge having the maximum length with respect to the length of an edge having the minimum length is 2 or less. And in addition, the tabular grains have monodispersibility. The monodispersibility is herein defined as the variation coefficient of the grain size distribution is 25% or less, preferably 20% or less, most preferably 15% or less. The variation coefficient is the value obtained by dividing a variation (standard deviation) in grain sizes represented by equivalent-circle diameters of projected areas of each of the grains, by their average of the grain sizes.
In the present invention, tabular grains preferably have dislocation lines.
Dislocation lines in tabular grains can be observed by a direct method performed at a low temperature using a transmission electron microscope, as described in, for example, J. F. Hamilton, Phot. Sci. Eng., 11, 57, (1967) or T. Shiozawa, J. Soc. Phot. Sci. Japan, 35, 213, (1972). That is, silver halide grains, extracted carefully from an emulsion so as not to apply a pressure at which dislocations are produced in the grains, are placed on a mesh for electron microscopic observation. Observation is performed by a transmission method while the sample is cooled to prevent damages (e.g., print out) due to electron rays. In this case, as the thickness of a grain is increased, it becomes more difficult to transmit electron rays through it. Therefore, grains can be observed more clearly by using an electron microscope of a high voltage type (200 kV or more for a grain having a thickness of 0.25 xcexcm). From photographs of grains obtained by the above method, it is possible to obtain the positions and the number of dislocations in each grain viewed in a direction perpendicular to the main surfaces of the grain.
Dislocations are produced from a position x% of the length between the center and the edge of a tabular grain to the edge in the major axis direction of the grain. The value of x is preferably 10xe2x89xa6x less than 100, more preferably 30xe2x89xa6x less than 98, and most preferably 50xe2x89xa6x less than 95. If this is the case, the shape obtained by connecting the start positions of the dislocations is almost similar to the shape of the grain. However, this shape is sometimes distorted, not perfectly similar. Dislocation lines are generally extended in a direction from the center to the edge but are sometimes zigzagged.
Grains containing five or more dislocations account for preferably 50% (in number) or more, and more preferably 80% (in number) of more. Most preferably, grains containing 10 or more dislocations account for 80% (in number) or more.
A method of manufacturing tabular grains used in the present invention will be described below.
Tabular grains used in the present invention can be prepared by the methods described in, e.g., Cleve, Photography Theory and Practice (1930), page 13; Gutoff, Photographic Science and Engineering, Vol. 14, pages 248 to 257, (1970); and U.S. Pat. No. 4,434,226, U.S. Pat. No. 4,414,310, U.S. Pat. No. 4,433,048, and U.S. Pat. No. 4,439,520, and British Patent 2,112,157, the disclosures of which are herein incorporated by reference.
A metal complex of Fe, Ru, Re, Os, Ir, Pt, or Au used in the present invention and containing at least two cyan ligands is preferably represented by formula (C-1) or (C-2) below:
[M1(CN)6-aLa]nxe2x80x83xe2x80x83(C-1) 
[M2(CN)4-bLb]mxe2x80x83xe2x80x83(C-2) 
(wherein
M1: Fe, Ru, Re, Os, Ir, or Pt
M2: Pt or Au
L: a ligand except for CN
a: 0, 1, or 2
b: 0, 1, or 2
n: 2-, 3-, or 4-
m: 1- or 2-)
Examples of a ligand except for CN, represented by L are F, Cl, Br, I, H2O, SCN, NO, pyrazole, imidazole and triazole.
A metal complex represented by formula (C-1) of the above two formulas is more preferably used. As M1 in formula (C-1), Fe, Ru, Re, Os, or Ir is preferable, and Fe is most preferable.
Practical examples of the metal complex used in the present invention and having at least two cyan ligands are presented below.
As counter ions of these metal complexes, ammonium ion, and alkali metal ions such as sodium and potassium ions are preferably used.
Though the metal complex in a form of ion as represented by formula (C-1) or (C-2) may exist in the tabular grains used in the invention, salts thereof with one of the counter ions can be added to prepare the tabular grains.
The content of the metal complex having at least two cyan ligands used in the present invention is preferably 1.0xc3x9710xe2x88x927 to 1.0xc3x9710xe2x88x923 mol, and more preferably 1.0xc3x9710xe2x88x925 to 5xc3x9710xe2x88x924 mol per mol of a silver halide.
It is preferable to dissolve these metal complexes in water or an appropriate solvent and directly add the resultant solution to a reaction solution during the formation of silver halide grains, or add the metal complexes to an aqueous halide solution, an aqueous silver salt solution, or some other solution for forming silver halide grains and perform grain formation. It is also preferable to dissolve silver halide fine grains containing these metal complexes and deposit the fine grains on other silver halide grains. There is no particular limited timing at which the metal complexed are added during the formation of the tabular grains.
When these metal complexes are added, the hydrogen ion concentration or pH of the reaction solution is preferably 1 to 10, and more preferably 3 to 7.
In addition to the metal complexes having at least two cyan ligands, silver halide grains used in the present invention preferably contain the following metal complexes or metal salts: hexachloroiridate(III) or (IV), hexaamineiridate(III) or (IV), trioxalatoiridate(III) or (IV), hexacyanoferrate(II) or (III), ferrous thiocyanate, and ferric thiocyanate.
The addition amount of the above iridium ion is preferably 10xe2x88x929 to 10xe2x88x926 mol, and most preferably 10xe2x88x928 to 10xe2x88x926 mol per mol of a silver halide. The addition amount of the above iron ion is preferably 10xe2x88x928 to 10xe2x88x924 mol, and most preferably 10xe2x88x927 to 10xe2x88x924 mol per mol of a silver halide.
When the present invention is applied to a color sensitive material, at least one sensitive layer needs only to be formed on a support. A typical example is a silver halide photographic light-sensitive material having, on its support, at least one sensitive layer constituted by a plurality of silver halide emulsion layers which are sensitive to essentially the same color but have different sensitivities. This sensitive layer is a unit sensitive layer sensitive to one of blue light, green light, and red light. In a multilayered silver halide color photographic light-sensitive material, such unit sensitive layers are generally arranged in the order of red-, green-, and blue-sensitive layers from a support. However, according to the intended use, this order of arrangement can be reversed, or sensitive layers sensitive to the same color can sandwich another sensitive layer sensitive to a different color. Non-sensitive layers can be formed between the silver halide sensitive layers and as the uppermost layer and the lowermost layer. These non-sensitive layers can contain, e.g., couplers, DIR compounds, and color-mixing inhibitors to be described later. As a plurality of silver halide emulsion layers constituting each unit sensitive layer, as described in DE1,121,470 or GB923,045, high- and low-speed emulsion layers are preferably arranged such that the sensitivity is sequentially decreased toward a support. In addition, as described in JP-A-57-112751, JP-A-62-200350, JP-A-62-206541, and JP-A-62-206543, the disclosures of which are herein incorporated by reference, layers can be arranged such that a low-speed emulsion layer is formed apart from a support and a high-speed layer is formed closer to the support.
More specifically, layers can be arranged from the farthest side from a support in the order of low-speed blue-sensitive layer (BL)/high-speed blue-sensitive layer (BH)/high-speed green-sensitive layer (GH)/low-speed green-sensitive layer (GL)/high-speed red-sensitive layer (RH)/low-speed red-sensitive layer (RL), the order of BH/BL/GL/GH/RH/RL, or the order of BH/BL/GH/GL/RL/RH.
In addition, as described in Jpn. Pat. Appln. KOKOKU Publication No. (hereafter referred to as JP-B-) 55-34932, layers can be arranged from the farthest side from a support in the order of blue-sensitive layer/GH/RH/GL/RL. Furthermore, as described in JP-A-56-25738 and JP-A-62-63936, the disclosures of which are herein incorporated by reference, layers can be arranged from the farthest side from a support in the order of blue-sensitive layer/GL/RL/GH/RH.
As described in JP-B-49-15495, the disclosure of which is herein incorporated by reference, three layers can be arranged such that a silver halide emulsion layer having the highest sensitivity is arranged as an upper layer, a silver halide emulsion layer having sensitivity lower than that of the upper layer is arranged as an interlayer, and a silver halide emulsion layer having sensitivity lower than that of the interlayer is arranged as a lower layer, i.e., three layers having different sensitivities can be arranged such that the sensitivity is sequentially decreased toward the support. When a layer structure is constituted by three layers having different sensitivities, these layers can be arranged in the order of medium-speed emulsion layer/high-speed emulsion layer/low-speed emulsion layer from the farthest side from a support in a layer sensitive to one color as described in JP-A-59-202464, the disclosure of which is herein incorporated by reference.
In addition, the order of high-speed emulsion layer/low-speed emulsion layer/medium-speed emulsion layer or low-speed emulsion layer/medium-speed emulsion layer/high-speed emulsion layer can be used. Furthermore, the arrangement can be changed as described above even when four or more layers are formed.
There is no particular limited layer to which the emulsion of the invention can be added.
In order to improve the color reproduction, a donor layer (CL) with an interlayer effect, which is described in U.S. Pat. No. 4,663,271, U.S. Pat. No. 4,705,744, U.S. Pat. No. 4,707,436, JP-A-62-160448, or JP-A-63-89850, the disclosures of which are herein incorporated by reference and different from the main sensitive layers BL, GL, and RL in spectral sensitivity distribution, is preferably formed adjacent to or close to the main sensitive layers.
The photographic light-sensitive material containing the emulsion of the invention can further contain following silver halide emulsion.
The silver halide used in the additional emulsion is silver iodobromide, silver iodochloride, or silver bromochloroiodide containing about 30 mol % or less of silver iodide. The silver halide is most preferably silver iodobromide or silver bromochloroiodide containing about 2 to about 10 mol % of silver iodide.
Silver halide grains contained in the additional photographic emulsion can have regular crystals such as cubic, octahedral, or tetradecahedral crystals, irregular crystals such as spherical or tabular crystals, crystals having crystal defects such as twin planes, or composite shapes thereof.
The silver halide can consist of fine grains having a grain size of about 0.2 xcexcm or less or large grains having a projected area diameter of up to about 10 xcexcm, and the emulsion can be either a polydisperse or monodisperse emulsion.
The silver halide photographic emulsion which can be used in the light-sensitive material of the present invention can be prepared by methods described in, for example, xe2x80x9cI. Emulsion preparation and types,xe2x80x9d Research Disclosure (RD) No. 17,643 (December, 1978), pp. 22 and 23, RD No. 18,716 (November, 1979), page 648, and RD No. 307105 (November, 1989), pp. 863 to 865; P. Glafkides, xe2x80x9cChemie et Phisique Photographiquexe2x80x9d, Paul Montel, 1967; G. F. Duffin, xe2x80x9cPhotographic Emulsion Chemistryxe2x80x9d, Focal Press, 1966; and V. L. Zelikman et al., xe2x80x9cMaking and Coating Photographic Emulsionxe2x80x9d, Focal Press, 1964, the disclosures of which are herein incorporated by reference.
Monodisperse emulsions described in, e.g., U.S. Pat. No. 3,574,628, U.S. Pat. No. 3,655,394, and GB1,413,748 are also preferred, the disclosures of which are herein incorporated by reference.
Tabular grains having an aspect ratio of 3 or more can also be used in the light-sensitive material of the present invention. Tabular grains can be easily prepared by methods described in Gutoff, xe2x80x9cPhotographic Science and Engineeringxe2x80x9d, Vol. 14, pp. 248 to 257 (1970); and U.S. Pat. No. 4,434,226, U.S. Pat. No. 4,414,310, U.S. Pat. No. 4,433,048, U.S. Pat. No. 4,439,520, and GB2,112,157, the disclosures of which are herein incorporated by reference.
A crystal structure can be uniform, can have different halogen compositions in the interior and the surface layer thereof, or can be a layered structure. Alternatively, a silver halide having a different composition can be bonded by an epitaxial junction or a compound except for a silver halide such as silver rhodanide or zinc oxide can be bonded. A mixture of grains having various types of crystal shapes can be used.
The above emulsion that can additionally be used in the light-sensitive material of the invention can be any of a surface latent image type emulsion which mainly forms a latent image on the surface of a grain, an internal latent image type emulsion which forms a latent image in the interior of a grain, and another type of emulsion which has latent images on the surface and in the interior of a grain. However, the emulsion must be a negative type emulsion. The internal latent image type emulsion can be a core/shell internal latent image type emulsion described in JP-A-63-264740, the disclosure of which is incorporated by reference. A method of preparing this core/shell internal latent image type emulsion is described in JP-A-59-133542, the disclosure of which is incorporated by reference. Although the thickness of a shell of this emulsion depends on, e.g., development conditions, it is preferably 3 to 40 nm, and most preferably 5 to 20 nm.
The silver halide emulsion used in the photographic material is normally subjected to physical ripening, chemical ripening, and spectral sensitization steps before it is used. Additives for use in these steps are described in RD Nos. 17,643, 18,716, and 307,105, the disclosures of which are herein incorporated by reference, and they are summarized in a table to be presented later.
In the sensitive material of the present invention, it is possible to mix, in a single layer, two or more types of emulsions different in at least one of characteristics of a sensitive silver halide emulsion, i.e., a grain size, a grain size distribution, a halogen composition, a grain shape, and sensitivity.
It is also possible to preferably use surface-fogged silver halide grains described in U.S. Pat. No. 4,082,553, internally fogged silver halide grains described in U.S. Pat. No. 4,626,498 and JP-A-59-214852, the disclosures of which are herein incorporated by reference, and colloidal silver, in at least one sensitive silver halide emulsion layer and/or at least one substantially non-sensitive hydrophilic colloid layer. The internally fogged or surface-fogged silver halide grain means a silver halide grain which can be developed uniformly (non-imagewise) regardless of whether the location is a non-exposed portion or an exposed portion of the sensitive material. A method of preparing the internally fogged or surface-fogged silver halide grain is described in U.S. Pat. No. 4,626,498 and JP-A-59-214852, the disclosures of which are herein incorporated by reference. A silver halide which forms the core of an internally fogged core/shell type silver halide grain can have a different halogen composition. As the internally fogged or surface-fogged silver halide, any of silver chloride, silver chlorobromide, silver bromoiodide, and silver bromochloroiodide can be used. The average grain size of these fogged silver halide grains is preferably 0.01 to 0.75 xcexcm, and most preferably 0.05 to 0.6 xcexcm. The grain shape can be a regular grain shape. Although the emulsion can be a polydisperse emulsion, it is preferably a monodisperse emulsion (in which at least 95% in weight or number of grains of silver halide grains have grain sizes falling within a range of xc2x140% of the average grain size).
In the photographic material of the present invention, it is preferable to use a non-light-sensitive fine grain silver halide. The non-light-sensitive fine grain silver halide preferably consists of silver halide grains which are not exposed during imagewise exposure for obtaining a dye image and are not substantially developed during development. These silver halide grains are preferably not fogged in advance. In the fine grain silver halide, the content of silver bromide is 0 to 100 mol %, and silver chloride and/or silver iodide can be added if necessary. The fine grain silver halide preferably contains 0.5 to 10 mol % of silver iodide. The average grain size (the average value of equivalent-circle diameters of projected areas) of the fine grain silver halide is preferably 0.01 to 0.5 xcexcm, and more preferably 0.02 to 0.2 xcexcm.
The fine grain silver halide can be prepared following the same procedures as for a common sensitive silver halide. In this case, the surface of each silver halide grain need not be optically sensitized nor spectrally sensitized. However, before the silver halide grains are added to a coating solution, it is preferable to add a well-known stabilizer such as a triazole-based compound, an azaindene-based compound, a benzothiazolium-based compound, a mercapto-based compound, or a zinc compound. Colloidal silver can be added to this fine grain silver halide grain-containing layer.
The silver coating amount of a sensitive material of the present invention is preferably 6.0 g/m2 or less, and most preferably 4.5 g/m2 or less.
Photographic additives usable in the present invention are also described in RDs, and the relevant portions, the disclosures of which are herein incorporated by reference, are summarized in the following table.
Various dye forming couplers can be used in a sensitive material of the present invention, and the following couplers are particularly preferable. The disclosures of the documents disclosing the couplers one herein incorporated by reference.
Yellow couplers: couplers represented by formulas (I) and (II) in EP502,424A; couplers (particularly Y-28 on page 18) represented by formulas (1) and (2) in EP513,496A; a coupler represented by formula (I) in claim 1 of Japanese Patent Application No. 4-134523; a coupler represented by formula (I) in column 1, lines 45 to 55, in U.S. Pat. No. 5,066,576; a coupler represented by formula (I) in paragraph 0008 of JP-A-4-274425; couplers (particularly D-35 on page 18) described in claim 1 on page 40 of EP498,381A1; couplers (particularly Y-1 (page 17) and Y-54 (page 41)) represented by formula (Y) on page 4 in EP447,969A1; and couplers (particularly II-17, II-19 (column 17), and II-24 (column 19)) represented by formulas (II) to (IV) in column 7, lines 36 to 58, in U.S. Pat. No. 4,476,219.
Magenta couplers: JP-A-3-39737 (L-57 (page 11, lower right column), L-68 (page 12, lower right column), and L-77 (page 13, lower right column); A-4 and A-63 (page 134), and A-4, A-73, and A-75 (page 139) in EP456,257; M-4 and M-6 (page 26), and M-7 (page 27) in EP486,965; M-45 in paragraph 0024 of Japanese Patent Application No. 4-234120; M-1 in paragraph 0036 of Japanese Patent Application No. 4-36917; and M-22 in paragraph 0237 of JP-A-4-362631.
Cyan couplers: CX-1, CX-3, CX-4, CX-5, CX-11, CX-12, CX-14, and CX-15 (pages 14 to 16) in JP-A-4204843; C-7 and C-10 (page 35), C-34 and C-35 (page 37), and (I-1) and (I-17) (pages 42 and 43) in JP-A-4-43345; and couplers represented by formulas (Ia) and (Ib) in claim 1 of Japanese Patent Application No. 4-236333.
Polymer couplers: P-1 and P-5 (page 11) in JP-A-2-44345.
Couplers for forming a colored dye with a proper diffusibility are preferably those described in U.S. Pat. No. 4,366,237, GB2,125,570, EP96,873B, and DE3,234,533.
Couplers for correcting unnecessary absorption of a colored dye are preferably yellow colored cyan couplers (particularly YC-86 on page 84) represented by formulas (CI), (CII), (CIII), and (CIV) described on page 5 in EP456,257A1; yellow colored magenta couplers ExM-7 (page 202), EX-1 (page 249), and EX-7 (page 251) in EP456,257A1; magenta colored cyan couplers CC-9 (column 8) and CC-13 (column 10) described in U.S. Pat. No. 4,833,069; (2) (column 8) in U.S. Pat. No. 4,837,136; and colorless masking couplers (particularly compound examples on pages 36 to 45) represented by formula (A) in WO92/11575.
Examples of a compound (including a coupler) which reacts with a developing agent oxidation product and releases a photographically useful compound residue are as follows. The disclosures of the references disclosing the compounds are herein incorporated by reference. Development inhibitor-releasing compounds: compounds (particularly T-101 (page 30), T-104 (page 31), T-113 (page 36), T-131 (page 45), T-144 (page 51), and T-158 (page 58)) represented by formulas (I), (II), (III), (IV) described on page 11 of EP378,236A1, compounds (particularly D-49 (page 51)) represented by formula (I) described on page 7 of EP436,938A2, compounds (particularly (23) in paragraph 0027) represented by formula (1) in Japanese Patent Application No. 4-134523, and compounds (particularly I-(1) on page 29) represented by formulas (I), (II), and (III) described on pages 5 and 6 of EP440,195A2; (Bleaching accelerator-releasing compounds: compounds (particularly (60) and (61) on page 61) represented by formulas (I) and (Ixe2x80x2) on page 5 of EP310,125A2, and compounds (particularly (7) (page 7)) represented by formula (I) in claim 1 of Japanese Patent Application No. 4-325564; ligand-releasing compound: compounds (particularly compounds in column 12, lines 21 to 41) represented by LIG-X described in claim 1 of U.S. Pat. No. 4,555,478; leuco dye-releasing compounds: compounds 1 to 6 in columns 3 to 8 of U.S. Pat. No. 4,749,641; fluorescent dye release compounds: compounds (particularly compounds 1 to 11 in columns 7 to 10) represented by COUP-DYE in claim 1 of U.S. Pat. No. 4,774,181; development accelerators- or fogging agent-releasing compounds: compounds (particularly (I-22) in column 25) represented by formulas (1), (2), and (3) in column 3 of U.S. Pat. No. 4,656,123, and ExZK-2 on page 75, lines 36 to 38, in EP450,637A2; compounds which release a group which does not function as a dye unless it splits off: compounds (particularly Y-1 to Y-19 in columns 25 to 36) represented by formula (I) in claim 1 of U.S. Pat. No. 4,857,447.
Preferable examples of additives other than couplers are as follows. The disclosures of the references disclosing the additives are herein incorporated by reference.
Dispersants of an oil-soluble organic compound: P-3, P-5, P-16, P-19, P-25, P-30, P-42, P-49, P-54, P-55, P-66, P-81, P-85, P-86, and P-93 (pages 140 to 144) in JP-A-62-215272; impregnating latexes of an oil-soluble organic compound: latexes described in U.S. Pat. No. 4,199,363; developing agent oxidation product scavengers: compounds (particularly I-(1), I-(2), I-(6), and I-(12) (columns 4 and 5)) represented by formula (I) in column 2, lines 54 to 62, in U.S. Pat. No. 4,978,606, and formulas (particularly a compound 1 (column 3)) in column 2, lines 5 to 10, in U.S. Pat. No. 4,923,787; stain inhibitors: formulas (I) to (III) on page 4, lines 30 to 33, particularly I-47, I-72, III-1, and III-27 (pages 24 to 48) in EP298321A; brown inhibitors: A-6, A-7, A-20, A-21, A-23, A-24, A-25, A-26, A-30, A-37, A-40, A-42, A-48, A-63, A-90, A-92, A-94, and A-164 (pages 69 to 118) in EP298321A, II-1 to III-23, particularly III-10, in columns 25 to 38 of U.S. Pat. No. 5,122,444, I-1 to III-4, particularly II-2, on pages 8 to 12 in EP471347A, and A-1 to A-48, particularly A-39 and A-42, in columns 32 to 40 of U.S. Pat. No. 5,139,931; materials which reduce the use amount of a color enhancer or a color-mixing inhibitor: I-1 to II-15, particularly I-46, on pages 5 to 24 in EP411324A; formalin scavengers: SCV-1 to SCV-28, particularly SCV-8, on pages 24 to 29 in EP477932A; film hardeners: H-1, H-4, H-6, H-8, and H-14 on page 17 in JP-A-1-214845, compounds (H-1 to H-54) represented by formulas (VII) to (XII) in columns 13 to 23 of U.S. Pat. No. 4,618,573, compounds (H-1 to H-76), particularly H-14, represented by formula (6) on page 8, lower right column, in JP-A-2-214852, and compounds described in claim 1 of U.S. Pat. No. 3,325,287; development inhibitor precursors: P-24, P-37, and P-39 (pages 6 and 7) in JP-A-62-168139; compounds described in claim 1, particularly 28 and 29 in column 7, of U.S. Pat. No. 5,019,492; antiseptic agents and mildewproofing agents: I-1 to III-43, particularly II-1, II-9, II-10, II-18, and III-25, in columns 3 to 15 of U.S. Pat. No. 4,923,790; stabilizers and antifoggants: I-1 to (14), particularly I-1, I-60, (2), and (13), in columns 6 to 16 of U.S. Pat. No. 4,923,793, and compounds 1 to 65, particularly a compound 36, in columns 25 to 32 of U.S. Pat. No. 4,952,483; chemical sensitizers: triphenylphosphine selenide and a compound 50 in JP-A-5-40324; dyes: a-1 to b-20, particularly a-1, a-12, a-18, a-27, a-35, a-36, and b-5, on pages 15 to 18 and V-1 to V-23, particularly V-1, on pages 27 to 29 in JP-A-3-156450, F-I-1 to F-II-43, particularly F-I-11 and F-II-8, on pages 33 to 55 in EP445627A, III-1 to III-36, particularly III-1 and III-3, on pages 17 to 28 in EP457153A, fine crystal dispersions of Dye-1 to Dye-124 on pages 8 to 26 in WO88/04794, compounds 1 to 22, particularly a compound 1, on pages 6 to 11 in EP319999A, compounds D-1 to D-87 (pages 3 to 28) represented by formulas (1) to (3) in EP519306A, compounds 1 to 22 (columns 3 to 10) represented by formula (I) in U.S. Pat. No. 4,268,622, and compounds (1) to (31) (columns 2 to 9) represented by formula (I) in U.S. Pat. No. 4,923,788; UV absorbents: compounds (18b) to (18r) and 101 to 427 (pages 6 to 9) represented by formula (1) in JP-A-46-3335, compounds (3) to (66) (pages 10 to 44) and compounds HBT-1 to HBT-10 (page 14) represented by formula (III) in EP520938A, and compounds (1) to (31) (columns 2 to 9) represented by formula (1) in EP521823A.
The present invention can be applied to various color sensitive materials such as color negative films for general purposes or movies, color reversal films for slides or television, color paper, color positive films, and color reversal paper. The present invention is also suited to film units with lens described in JP-B-2-32615 and Jpn. UM Appln. KOKOKU Publication No. 3-39784. Furthermore, the present invention is applicable to black-and-white sensitive materials such as black-and-white negative films and X-ray films.
A support which can be suitably used in the present invention is described in, e.g., RD. No. 17643, page 28, RD. No. 18716, from the right column, page 647 to the left column, page 648, and RD. No. 307105, page 879.
In a sensitive material of the present invention, the total film thickness of all hydrophilic colloid layers on the side having emulsion layers is preferably 28 xcexcm or less, more preferably 23 xcexcm or less, particularly preferably 18 xcexcm or less, and most preferably 16 xcexcm or less. A film swell speed Txc2xd is preferably 30 sec or less, and more preferably, 20 sec or less. Txc2xd is defined as a time which the film thickness requires to reach xc2xd of a saturation film thickness which is 90% of a maximum swell film thickness reached when processing is performed by using a color developer at 30xc2x0 C. for 3 min and 15 sec. The film thickness means the thickness of a film measured under moisture conditioning at a temperature of 25xc2x0 C. and a relative humidity of 55% (two days). Txc2xd can be measured by using a swell meter described in Photogr. Sci. Eng., A. Green et al., Vol. 19, No. 2, pp. 124 to 129. Txc2xd can be adjusted by adding a film hardening agent to gelatin as a binder or changing aging conditions after coating. The swell ratio is preferably 150 to 400%. The swell ratio can be calculated from the maximum swell film thickness under the conditions mentioned above by using (maximum swell film thicknessxe2x88x92film thickness)/film thickness.
In a sensitive material of the present invention, hydrophilic colloid layers (called back layers) having a total dried film thickness of 2 to 20 xcexcm are preferably formed on the side opposite to the side having emulsion layers. The back layers preferably contain, e.g., the light absorbent, the filter dye, the ultraviolet absorbent, the antistatic agent, the film hardener, the binder, the plasticizer, the lubricant, the coating aid, and the surfactant described above. The lubrication ratio of the back layers is preferably 150% to 500%.
A color sensitive material according to the present invention can be developed by conventional methods described in RD. No. 17643, pp. 28 and 29, RD. No. 18716, page 615, the left to right columns, and RD No. 307105, pp. 880 and 881.
A color developer used in the development of a sensitive material of the present invention is preferably an aqueous alkaline solution mainly consisting of an aromatic primary amine-based color developing agent. As this color developing agent, although an aminophenol-based compound is effective, a p-phenylenediamine-based compound is preferably used. Typical examples and preferable examples of the p-phenylenediamine-based compound are compounds described in EP556700A, page 28, lines 43 to 52. These compounds can be used in a combination of two or more thereof in accordance with the application.
In general, the color developer contains a pH buffering agent such as a carbonate, a borate, or a phosphate of an alkali metal, and a development restrainer or an antifoggant such as a bromide, an iodide, a benzimidazole, a benzothiazole, or a mercapto compound. If necessary, the color developer can also contain a preservative such as hydroxylamine, diethylhydroxylamine, hydrazine compounds such as N,N-biscarboxymethyl hydrazine, a sulfite, a phenylsemicarbazide, triethanolamine, or a catechol sulfonic acid; an organic solvent such as ethyleneglycol or diethyleneglycol; a development accelerator such as benzylalcohol, polyethyleneglycol, a quaternary ammonium salt or an amine; a dye forming coupler; a competing coupler; an auxiliary developing agent such as 1-phenyl-3-pyrazolidone; a viscosity imparting agent; and a chelating agent represented by aminopolycarboxylic acid, an aminopolyphosphonic acid, an alkylphosphonic acid, or a phosphonocarboxylic acid. Examples of the chelating agent are ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N,N-tetramethylenephosphonic acid, and ethylenediamine-di(o-hydroxyphenylacetic acid), and salts thereof.
In order to perform reversal development, color development is usually performed after black-and-white development is performed. As a black-and-white developer, well-known black-and-white developing agents, e.g., a dihydroxybenzene such as hydroquinone, a 3-pyrazolidone such as 1-phenyl-3-pyrazolidone, and an aminophenyl such as N-methyl-p-aminophenol can be used singly or in combination of two or more types thereof. The pH of the color and black-and-white developers is generally 9 to 12. Although the quantity of replenisher of these developers depends on a color photographic sensitive material to be processed, it is generally 3 L (liter) or less per m2 of the sensitive material. The quantity of replenisher can be decreased to 500 mL or less by decreasing the bromide ion concentration in the replenisher. In order to decrease the quantity of replenisher, the contact area of a processing tank with air is preferably decreased to prevent evaporation and oxidation of the replenisher by air.
The processing effect resulting from the contact between the photographic processing solution and air in the processing tank can be evaluated by an aperture (=[contact area (cm2) between processing solution and air]÷[volume (cm3) of processing solution]). This aperture is preferably 0.1 or less, and more preferably 0.001 to 0.05. In order to reduce the aperture, a shielding member such as a floating cover can be provided on the liquid surface of the photographic processing solution in the processing tank. In addition, a method of using a movable cover described in JP-A-1-82033 or a slit developing method descried in JP-A-63-216050 can be used. The aperture is preferably reduced not only in color and black-and-white development steps but also in all subsequent steps, e.g., bleaching, bleach-fixing, fixing, washing, and stabilizing steps. In addition, the quantity of replenisher can be reduced by using means for suppressing storage of bromide ions in the developing solution.
The color development time is normally two to five minutes. The processing time, however, can be shortened by setting a high temperature and a high pH and using the color developing agent at a high concentration.
The color-developed photographic emulsion layer is generally bleached. Bleaching can be performed either simultaneously with fixing (bleach-fixing) or independently thereof. In addition, in order to increase the processing speed, bleach-fixing can be performed after bleaching. Also, processing can be performed in a bleach-fixing bath having two continuous tanks, fixing can be performed before bleach-fixing, or bleaching can be performed after bleach-fixing, according to the intended use. Examples of the bleaching agent are a compound of a multivalent metal such as iron(III), peroxides, quinones, and a nitro compound. Typical examples of the bleaching agent are an organic complex salt of iron(III), e.g., a complex salt of an aminopolycarboxylic acid such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, and 1,3-diaminopropanetetraacetic acid, and glycoletherdiaminetetraacetic acid; or a complex salt of citric acid, tartaric acid, or malic acid. Of these compounds, an iron(III) complex salt of aminopolycarboxylic acid such as an iron(III) complex salt of ethylenediaminetetraacetic acid or 1,3-diaminopropanetetraacetic acid is preferred because it can increase the processing speed and prevent the environmental contamination. The iron(III) complex salt of aminopolycarboxylic acid is useful in both the bleaching and bleach-fixing solutions. The pH of the bleaching or bleach-fixing solution using the iron(III) complex salt of aminopolycarboxylic acid is normally 4.0 to 8. In order to increase the processing speed, however, the processing can be performed at a lower pH.
A bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution, and their pre-bath, if necessary. Useful examples of the bleaching accelerator are: compounds having a mercapto group or a disulfide group described in, e.g., U.S. Pat. No. 3,893,858, DE1,290,812, DE2,059,988, JP-A-53-32736, JP-A-53-57831, JP-A-53-37418, JP-A-53-72623, JP-A-53-95630, JP-A-53-95631, JP-A-53-104232, JP-A-53-124424, JP-A-53-141623, JP-A-53-28426, and RD No. 17129 (July, 1978); a thiazolidine derivative described in JP-A-50-140129; thiourea derivatives described in JP-B-45-8506, JP-A-52-20832, JP-A-53-32735, and U.S. Pat. No. 3,706,561; iodide salts described in DE1,127,715 and JP-A-58-16235; polyoxyethylene compounds descried in DE966,410 and DE2,748,430; a polyamine compound described in JP-B-45-8836; compounds descried in JP-A-49-40943, JP-A-49-59644, JP-A-53-94927, JP-A-54-35727, JP-A-55-26506, and JP-A-58-163940; and bromide ion. Of these compounds, a compound having a mercapto group or a disulfide group is preferable since the compound has a large accelerating effect. In particular, compounds described in U.S. Pat. No. 3,893,858, DE1,290,812, and JP-A-53-95630 are preferred. A compound described in U.S. Pat. No. 4,552,834 is also preferable. These bleaching accelerators can be added in the sensitive material. These bleaching accelerators are useful especially in bleach-fixing of a photographic color sensitive material.
The bleaching solution or the bleach-fixing solution preferably contains, in addition to the above compounds, an organic acid in order to prevent a bleaching stain. The most preferable organic acid is a compound having an acid dissociation constant (pKa) of 2 to 5, for example, acetic acid, propionic acid, or hydroxyacetic acid.
Examples of the fixing agent are a thiosulfate, a thiocyanate, a thioether-based compound, thioureas, and a large amount of an iodide. Of these compounds, a thiosulfate is generally used, and especially ammonium thiosulfate can be used in the widest range of applications. In addition, a combination of a thiosulfate and a thiocyanate, a thioether-based compound, or thiourea is preferably used. As a preservative of the bleach-fixing solution, a sulfite, a bisulfite, a carbonyl bisulfite adduct, or a sulfinic acid compound described in EP294769A is preferred. In addition, in order to stabilize the fixing solution or the bleach-fixing solution, various types of aminopolycarboxylic acids or organic phosphonic acids are preferably added to the solution.
In the present invention, a compound having a pKa of 6.0 to 9.0 in concentrations of 0.1 to 10 mol/L of the fixing solution or the bleach-fixing solution are preferably added to the solution in order to adjust the pH. Preferable examples of the compound are imidazoles such as imidazole, 1-methylimidazole, 1-ethylimidazole, and 2-methylimidazole.
The total time of a desilvering step is preferably as short as possible as long as no desilvering defect occurs. A preferable time is one to three minutes, and more preferably, one to two minutes. A processing temperature is 25xc2x0 C. to 50xc2x0 C., and preferably 35xc2x0 C. to 45xc2x0 C. Within the preferable temperature range, the desilvering speed increases, and generation of a stain after the processing can be effectively prevented.
In the desilvering step, stirring is preferably as strong as possible. Examples of a method of strengthening the stirring are a method of colliding a jet stream of the processing solution against the emulsion surface of the sensitive material described in JP-A-62-183460, a method of increasing the stirring effect using rotating means described in JP-A-62-183461, a method of moving the sensitive material while the emulsion surface is brought into contact with a wiper blade provided in the solution to cause disturbance on the emulsion surface, thereby improving the stirring effect, and a method of increasing the circulating flow amount in the overall processing solution. Such a stirring improving means is effective in any of the bleaching solution, the bleach-fixing solution, and the fixing solution. It is assumed that the improvement in stirring increases the speed of supply of the bleaching agent and the fixing agent into the emulsion film to lead to an increase in desilvering speed. The above stirring improving means is more effective, e.g., can significantly increase the accelerating speed or eliminate fixing interference caused by the bleaching accelerator when the bleaching accelerator is used.
An automatic processor for processing a sensitive material of the present invention preferably has a sensitive material conveyor means described in JP-A-60-191257, JP-A-191258, or JP-A-60-191259. As described in JP-A-60-191257, this conveyor means can significantly reduce carry-over of a processing solution from a pre-bath to a post-bath, thereby effectively preventing degradation in performance of the processing solution. This effect significantly shortens especially the processing time in each processing step and reduces the processing solution replenishing amount.
The sensitive material of the present invention is normally subjected to washing and/or stabilizing steps after desilvering. An amount of water used in the washing step can be arbitrarily determined over a broad range in accordance with the properties (e.g., a property determined by use of a coupler) of the sensitive material, the intended use of the material, the temperature of the water, the number of water tanks (the number of stages), a replenishing scheme representing a counter or forward current, and other conditions. The relationship between the amount of water and the number of water tanks in a multi-stage counter-current scheme can be obtained by a method described in xe2x80x9cJournal of the Society of Motion Picture and Television Engineeringxe2x80x9d, Vol. 64, PP. 248-253 (May, 1955). According to the above-described multi-stage counter-current scheme, the amount of water used for washing can be greatly decreased. Since washing water stays in the tanks for a long period of time, however, bacteria multiply and floating substances can be undesirably attached to the sensitive material. In order to solve this problem in the process of the color photographic sensitive material of the present invention, a method of decreasing calcium and magnesium ions can be effectively utilized, as described in JP-A-62-288838. In addition, a germicide such as an isothiazolone compound and cyabendazole described in JP-A-57-8542, a chlorine-based germicide such as chlorinated sodium isocyanurate, and germicides such as benzotriazole described in Hiroshi Horiguchi et al., xe2x80x9cChemistry of Antibacterial and Antifungal Agentsxe2x80x9d, (1986), Sankyo Shuppan, Eiseigijutsu-Kai ed., xe2x80x9cSterilization, Antibacterial, and Antifungal Techniques for Microorganismsxe2x80x9d, (1982), Kogyogijutsu-Kai, and Nippon Bokin Bokabi Gakkai ed., xe2x80x9cDictionary of Antibacterial and Antifungal Agentsxe2x80x9d, (1986).
The pH of the water for washing the photographic sensitive material of the present invention is 4 to 9, and preferably 5 to 8. The water temperature and the washing time can vary in accordance with the properties and the intended use of the sensitive material. Normally, the washing time is 20 seconds to 10 minutes at a temperature of 15xc2x0 C. to 45xc2x0 C., and preferably 30 seconds to 5 minutes at 25xc2x0 C. to 40xc2x0 C. A sensitive material of the present invention can be processed directly by a stabilizing agent in place of washing. All known methods described in JP-A-57-8543, JP-A-58-14834, and JP-A-60-220345 can be used in such stabilization processing.
Stabilization is sometimes performed subsequently to washing. One example is a stabilizing bath containing a dye stabilizing agent and a surface-active agent to be used as a final bath of the photographic color sensitive material. Examples of the dye stabilizing agent are an aldehyde such as formalin and glutaraldehyde, an N-methylol compound, hexamethylenetetramine, and an aldehyde sulfurous acid adduct. Various chelating agents or antifungal agents can be added to the stabilizing bath.
An overflow solution produced upon washing and/or replenishment of the stabilizing solution can be reused in another step such as a desilvering step.
In the processing using an automatic processor or the like, if each processing solution described above is condensed by evaporation, water is preferably added to correct condensation.
The silver halide color sensitive material of the present invention can contain a color developing agent in order to simplify processing and increase the processing speed. For this purpose, various types of precursors of a color developing agent can be preferably used. Examples of the precursor are an indoaniline-based compound described in U.S. Pat. No. 3,342,597, Schiff base compounds described in U.S. Pat. No. 3,342,599 and RD Nos. 14850 and 15159, an aldol compound described in RD No. 13924, a metal salt complex described in U.S. Pat. No. 3,719,492, and a urethane-based compound described in JP-A-53-135628.
A sensitive material of the present invention can contain various 1-phenyl-3-pyrazolidones in order to accelerate color development, if necessary. Typical examples of the compound are described in JP-A-56-64339, JP-A-57-144547, and JP-A-58-115438.
Each processing solution in the present invention is used at a temperature of 10xc2x0 C. to 50xc2x0 C. Although a normal processing temperature is 33xc2x0 C. to 38xc2x0 C., processing can be accelerated at a higher temperature to shorten the processing time, or the image quality or stability of a processing solution can be improved at a lower temperature.
Various additives and developing methods are not particularly limited when the present invention is applied to black-and-white sensitive materials. For example, additives and methods described in the following portions of JP-A-2-68539, JP-A-5-11389, and JP-A-2-58041 can be preferably used.
1. Silver halide emulsions and manufacturing methods: JP-A-2-68539, page 8, lower right column, line 6 from the bottom to page 10, upper right column, line 12.
2. Chemical sensitization methods: JP-A-2-68539, page 10, upper right column, line 13 to lower left column, line 16, and a selenium sensitization method described in JP-A-5-11389.
3. Antifoggants and stabilizers: JP-A-2-68539, page 10, lower left column, line 17 to page 11, upper left column, line 7 and page 3, lower left column, line 2 to page 4, lower left column.
4. Spectral sensitizing dyes: JP-A-2-68539, page 4, lower right column, line 4 to page 8, lower right column and JP-A-2-58041, page 12, lower left column, line 8 to lower right column, line 19.
5. Surfactants and antistatic agents: JP-A-2-68539, page 11, upper left column, line 14 to page 12, upper left column, line 9 and JP-A-2-58041, page 2, lower left column, line 14 to page 5, line 12.
6. Matting agents, plasticizers, and slip agents: JP-A-2-68539, page 12, upper left column, line 10 to upper right column, line 10 and JP-A-2-58041, page 5, lower left column, line 13 to page 10, lower left column, line 3.
7. Hydrophilic colloids: JP-A-2-68539, page 12, upper right column, line 11 to lower left column, line 16.
8. Film hardeners: JP-A-2-68539, page 12, lower left column, line 17 to page 13, upper right column, line 6.
9. Development methods: JP-A-2-68539, page 15, upper left column, line 14 to lower left column, line 13.
The present invention is also applicable to heat development sensitive materials described in, e.g., U.S. Pat. No. 4,500,626, JP-A-60-133449, JP-A-59-218443, JP-A-61-238056, and EP210,660A2.
A silver halide sensitive material carrying magnetic recording layer and usable in the present invention can be any material provided that the material has a magnetic recording layer. This magnetic recording layer is formed adjacent to a support or formed via another photographic constituent layer.
The magnetic recording layer can also be a stripe layer described in JP-A-4-124642 or JP-A-4-124645.
As the magnetic recording layer, it is possible to use coating of ferromagnetic grains described in JP-A-59-23505, JP-A-4-195726, and JP-A-6-59357.
If this is the case, silver halide emulsions described in JP-A-4-166932, JP-A-3-41436, and JP-A-3-41437 can be used.
As a support, it is possible to use triacetate cellulose or polyethyleneterephthalate which is transparent and conventionally used in color films. However, the use of polyethylene aromatic dicarboxylate-based polyester supports is preferable in terms of magnetic recording characteristics. Polyethyleneterephthalate is particularly preferable among other polyethylene aromatic dicarboxylate-based polyester supports.
The thickness of this support is 50 to 300 xcexcm, preferably 50 to 200 xcexcm, more preferably 80 to 115 xcexcm, and most preferably 85 to 105 xcexcm.
As the support, it is preferable to use annealed polyester thin-film supports described in detail in JP-A-6-35118, JP-A-6-17528, and JIII Journal of Technical Disclosure No. 94-6023. More specifically, a support annealed at from 40xc2x0 C. to a glass transition point for 1 to 1,500 hrs is preferable.
The above support can be further subjected to surface treatments such as ultraviolet radiation described in JP-B-43-2603, JP-B-43-2604, and JP-B-45-3828, corona discharge described in JP-B-48-5043 and JP-A-51-131576, and glow discharge described in JP-B-35-7578 and JP-B-46-43480. It is also possible to perform undercoating described in U.S. Pat. No. 5,326,689, form an underlayer described in U.S. Pat. No. 2,761,791 where necessary, and perform antistatic processing described in JP-A-4-62543 where necessary.
It is preferable to manufacture the above sensitive material by a manufacturing management method described in JP-B-4-86817 and record the manufacturing data by a method described in JP-B-6-87146. After or before that, the sensitive material is cut into a narrower film than the conventional 135 size in accordance with a method described in JP-A-4-125560. Two perforations are formed on each side of each small-format frame thus obtained such that the perforations match this small-format frame smaller than the conventional frames.
The resultant film can be used by placing it into a cartridge package described in JP-A-4-157459, a cartridge shown in FIG. 9 of an embodiment described in JP-A-5-210202, a film patrone described in U.S. Pat. No. 4,221,479, or a cartridge described in U.S. Pat. No. 4,834,308, U.S. Pat. No. 4,834,366, U.S. Pat. No. 5,226,613, or U.S. Pat. No. 4,846,418.
The film cartridge or film patrone herein used is preferably a type capable of accommodating the tongue of a film as described in U.S. Pat. No. 4,848,893 or U.S. Pat. No. 5,317,355 in respect of light-shielding properties.
It is more preferable to use a cartridge with a locking mechanism as described in U.S. Pat. No. 5,296,886, a cartridge displaying the use state described in U.S. Pat. No. 5,347,334, or a cartridge with a double exposure preventing function.
Also, as described in JP-A-6-85128, it is possible to use a cartridge by which a film is easily loaded by simply inserting the film into the cartridge.
A film cartridge thus manufactured can be purposefully used in photography, development, and various photographic pleasures by using cameras, processors, and laboratory machines described below.
For example, the function of a film cartridge (patrone) can be well achieved by using an easy-loading camera described in JP-A-6-8886 or JP-A-6-99908, an auto-winding camera described in JP-A-6-57398 or JP-A-6-101135, a camera described in JP-A-6-205690 by which a film can be unloaded and replaced during photography, a camera described in JP-A-5-283382 by which the information of photography such as panorama photography, Hivision photography, or normal photography can be magnetically recorded on a film (i.e., the printing aspect ratio is selectable and magnetically recordable), a camera with a double exposure preventing function described in JP-A-6-101194, and a camera with a function of displaying the use state of a film or the like described in JP-A-5-150577.
A photographed film can be processed by an automatic processor described in JP-A-6-222514 or JP-A-6-222545. Alternatively, before, during, or after the processing it is possible to use a method of using magnetically recorded information on a film described in JP-A-6-95265 or JP-A-4-123054 or use an aspect ratio selecting function described in JP-A-5-19364.
If the development is motion picture type development, films are spliced by a method described in JP-A-5-119461.
During or after the development, attaching and detaching described in JP-A-6-148805 are performed.
After the above processes, film information can also be changed to a print through back printing or front printing to color paper described in JP-A-2-184835, JP-A-4-186335, or JP-A-6-79968.
Furthermore, a film can be returned to the customer with an index print described in JP-A-5-11353 or JP-A-5-232594 and a return cartridge.